Effect of chemical substitution on the ionization potentials and electron affinity of systems with conjugated bonds

Vysotskii, Yu. B.

doi:10.1007/bf00518439

Cited by 3 publications

(3 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Specifically, one should aim to reduce the EA further for the anion group and to reduce the transition energy of the charge-transfer state. Possible modification could include the incorporation of hydroxyl groups that have been observed to lower the EA in substituted benzene derivatives [ 49 ]. Alternatively, on might consider attaching a nearby chromophore whose excited state has a similar energy to the π* MO on the nucleobase to affect charge-transfer.…”

Section: Discussionmentioning

confidence: 99%

Intramolecular Photo-Oxidation as a Potential Source to Probe Biological Electron Damage: A Carboxylated Adenosine Analogue as Case Study

Castellani

Verlet

2021

Molecules

View full text Add to dashboard Cite

A carboxylated adenosine analog (C-Ado−) has been synthesized and probed via time-resolved photoelectron spectroscopy in order to induce intra-molecular charge transfer from the carboxylic acid moiety to the nucleobase. Intra-molecular charge transfer can be exploited as starting point to probe low-energy electron (LEE) damage in DNA and its derivatives. Time-dependent density functional theory (TD-DFT) calculations at the B3LYP-6311G level of theory have been performed to verify that the highest occupied molecular orbital (HOMO) was located on carboxylic acid and that the lowest occupied molecular orbital (LUMO) was on the nucleobase. Hence, the carboxylic acid could work as electron source, whilst the nucleobase could serve the purpose of electron acceptor. The dynamics following excitation at 4.66 eV (266 nm) were probed using time-resolved photoelectron spectroscopy using probes at 1.55 eV (800 nm) and 3.10 eV (400 nm). The data show rapid decay of the excited state population and, based on the similarity of the overall dynamics to deoxy-adenosine monophosphate (dAMP–), it appears that the dominant decay mechanism is internal conversion following 1ππ* excitation of the nucleobase, rather than charge-transfer from the carboxylic acid to the nucleobase.

show abstract

Section: Discussionmentioning

confidence: 99%

Intramolecular Photo-Oxidation as a Potential Source to Probe Biological Electron Damage: A Carboxylated Adenosine Analogue as Case Study

Castellani

Verlet

2021

Molecules

View full text Add to dashboard Cite

show abstract

“…In addition, earlier one of the authors of the present study developed a quantum chemical scheme for accounting the impact of substituents on the physical-chemical properties of molecules with conjugated bonds: thermodynamic, electric, magnetic, spectral (UV, EPR, NMR, H1, C13-spectra), ionization potentials, electron affinity, pK a and other (see for example, ref. [31][32][33]. The scheme is based on the assumption that the impact of the substituent can be described using only one semiempirical parameter Da (variation of the effective electronegativity of the atom, to which the substituent is attached).…”

Section: Modelmentioning

confidence: 99%

Quantum chemical clarification of the alkyl chain length threshold of nonionic surfactants for monolayer formation at the air/water interface

Vysotsky

Kartashynska

Belyaeva

et al. 2016

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

A theoretical basis is provided for the experimental fact that for various surfactant classes the alkyl chain length threshold varies for the formation of condensed monolayers. The existence of the alkyl chain length threshold for a surfactant enabling the formation of monolayers is determined by the entropy increment to the Gibbs' energy, assessed by using the quantum chemical semiempiric method PM3. The value of the clusterization threshold is not stipulated by the surfactant solubility in water, rather by the electron-donor and electron-seeking properties of the head groups. These properties in turn impact the value of the solubility threshold for surfactants. The value of the clusterization threshold depends quadratically on the substituent constants, i.e. it is independent of whether the functional group is a donor or an acceptor of electrons. Rather it depends only on the donor or the acceptor 'force' of the substituent. The square-law dependence of the surface clusterization threshold of the amphiphile on the solubility threshold is evidenced.

show abstract

“…The presence of functional groups leads to a change in the rate of rearrangement, determined by the size of ∆α j , characterizing the substituent (their values are tabulated in [19]), and the mutual polarizability π j,ik between atom j at the place of introduction of the functional group and the bond ik at which cyclization proceeds.…”

mentioning

confidence: 99%

Quantum-chemical interpretation of cyclization and recyclization reactions. 27. Electrocyclization of phenyl derivatives and benzoannelated derivatives of 1,2,4-triazahexa-1,3,5-triene and 1,2,4-oxadiazahexa-1,3,5-triene

Vysotskii

Бузыкин

Bryantsev

2006

Chem Heterocycl Compd

Self Cite

View full text Add to dashboard Cite

Effect of chemical substitution on the ionization potentials and electron affinity of systems with conjugated bonds

Cited by 3 publications

References 10 publications

Intramolecular Photo-Oxidation as a Potential Source to Probe Biological Electron Damage: A Carboxylated Adenosine Analogue as Case Study

Intramolecular Photo-Oxidation as a Potential Source to Probe Biological Electron Damage: A Carboxylated Adenosine Analogue as Case Study

Quantum chemical clarification of the alkyl chain length threshold of nonionic surfactants for monolayer formation at the air/water interface

Quantum-chemical interpretation of cyclization and recyclization reactions. 27. Electrocyclization of phenyl derivatives and benzoannelated derivatives of 1,2,4-triazahexa-1,3,5-triene and 1,2,4-oxadiazahexa-1,3,5-triene

Contact Info

Product

Resources

About